Hair-waving composition



. the quality of odor of the perfume.

Patented June 17, 1952 UNITED STATES PATENT OFFICE HAIR-WAVING COMPOSITION Menotti Del Zoppo, New York, N. Y., assignor of one-half to Alice Parker, New York, N. Y.

No Drawing. Application March 15, 1950,

Serial No. 149,899

7 Claims. (of lea-87.1)

these solutions are generally satisfactory, there are certain disadvantages in them. Thioglycolic acid has a strong, objectionable odor. The thioglycolic acid is unstable in contact with air. Thioglycolic acid itself is a liquid and the lotions are necessarily shipped in liquid tight containers, such as bottles, with attendant expense in the original cost of the containers, filling the containers, capping them, packing them for shipment, and then paying freight on a solution which is ordinarily 85% to 90% water. Finally, the thioglycolic acid lotions cause overtreatment of the hair unless the treatment is discontinued at the proper time, a fact'which is generally recognized, and is emphasized by one manufacturer who includes in his package a specialfldial for reading off the time for treatment of hair of different classes. v

I have now discovered that these objections are overcome and that I may obtain a good, satisfactory waving effect by the use of any one of several polythio compounds of kind to be describedherein. These compounds are either entirely odorless or are so nearly odorless that they may be perfumed to establish what is in effect They are solids. They may be shipped in special paper envelopes, instead of bottles or the like, and dissolved at or only shortly before the time of use. They are stable in contact with oxygen or air at ordinary temperatures. They seem to provide a buffer vor like effect which practically eliminates the danger of overtreating the hair in normal use of the compositions.

Briefly stated, the invention comprises a hair waving composition including as the keratin softening agent a thiocarbonic acid ester of glycolic acid or like alpha-hydroxy fatty acid in conjunction with an amine in amount to establish the pH within the range 8 to 10. The invention comprises, also, the herein described method of waving hair by contacting it with the keratin softening agent of kind described and then removing thesaid agent.

In one embodiment, the invention comprises a waving composition including an alkali metal salt of the thiocarbonic acid derivative in conjunction with a surface active agent.

In a modification, the invention comprises a waving composition of the kind described and an enhancing agent to increase the effectiveness on human hair, the enhancing agent being a compound of mild reducing properties of which examples are ascorbic acid, sorbose, and glucose. For this purpose, the ascorbic acid is preferred.

As the thiocarbonic acid ester used as the kera tin softening agent, I employ an ester of an alpha-hydroxy fatty acid with another acid selected from the group consisting of dior trithiocarbonlc acid and dithiocarbamic acid. In

the case of the dithiocarbonic acid, one of the acid hydrogens may be replaced by the radical ered hypothetically as derived from carbonic acid by replacing the proper number of oxygen atoms by sulfur atoms, to give the dior trithio-derivatives and then reacting the thiocarbonic acid with a hydroxyl attached to a OH or CH2 group in the alpha-hydroxy fatty acid, to give an ester with the hydroxy acid. Actuallyfthis isnot the way the esters are made but this consideration tends to simplify the understanding of the structure of the compounds. It will be seen that there will be left, in such esters, a free carboxyl group or groups which are available for formin salts with amines or other alkalies.

The. examples of compounds illustrating the various classes of derivatives before neutralizing the carboxyl groups are the following:

(1) some 00H s=o e scmo 0 on Glycolic acid ester of trithiocarbonic acid 2 ooH,oooH somcoon s=o v or 0=o somcoon scmooofl Qlycqlle semester oi slltlalorssbeslr acid S CHzC 0H Mixed ester of dithio carbonic acid S 0 H2 0 O O H Dlthiocarbamic ester of glycolic acid In the Formula 3 above, R stands for a lower alkyl group such as one containing 1 to4 carbon atoms. In Formula 4, R stands for an amine group, an alkyl substituted amine group, or a cyclic amine group of which examples are NHz, N(CH3)2, N(C2H5)2, N(C3H'z) 2, and NC4H80 (morpholine radical).

In general the keratin softening agents are compounds of the class described that, in the form of simple amine or alkali metal salts are water soluble, stable in dry form and non-irritat ing and non-toxic under conditions of use. The agents must be stable in dry form. In the preferred embodiment of the invention, in which the softening agents are to be shipped in solid form the keratin softening agents must be themselves solids at ordinary temperatures.

As the alkali which is used to make the salt, by neutralizing the free carboxyl groups of compounds (esters) of the class shown above, there are used water'soluble amines. Examples are methyl, ethyl, isopropyl and butylamines; alkylolamines such as ethanol, propanol, isopropanol, or butanol amines in the form of the mono-, di-, or tri-products of which monoisopropanolamine, diisopropanolaminev and triisopropanolamines are examples; aminoethyl ethanolamine; tris-hydroxy methyl aminomethane; 2-amino 2-methyl 1-propanol; and cyclic amines such as morpholine, piperazine, and the like.

The alkali metal alkalies may be used to give the salts of thethio esters referredtoabovebut the resulting salts are not as effective in waving hair as the amine salts. When alkali metal al kalies are used, a surface active agent' is also incorporated to increase the rate of softening of keratin. Preferably an enhancing agent of the kind described, as, for instance, ascorbic acid is introduced'to improve the waving properties.

For convenience in shipping, I may form a mixture'of (1) the thio ester of the alpha-hydroxy carb'oxylic acid and (*2) the salt of an amine, such as one of those described, with a mineral acid of which examples are hydrochloric sulfuric, boric, or phosphoric. In such a mixture, the amineis liberated from its, salt just before use by the addition of a caustic alkali preferably in approximately equivalent proportion. The amine so liberated is then free to react'with the carboxyl groups of the thio ester, to-form the amine salt waving compound.

Thus I may form, for shipment in paper envelopes, a mixture of the thio ester or keratin softening agent of kind described with monoisopropanolamine hydrochloride or other salt of the selected amine. Then, before the mixture of the keratin softening agent and the amine hydrochloride or the like is applied to the hair, the mixture is dissolved, along with lithium, sodium or potassium hydroxide or like alkali in proportion equivalent to the amine represented in the mixture. Alkali so added displaces the amine from thehydrochlorideor like salt, togive the free amine which then reacts at once, to form a salt with the thio ester. The result is the replacement of hydrogen of the carboxyl groups in the formulas given above by amine groups of which the monoisopropanolamine is particularly satisfactory.

It will be understoodthat the lithium or like alkali for the amine liberation may be shipped in a waterproof and alkali-proof container such as a sealed bag of plastic, as polyethylene.

It will be understood also that the thio esters which, in' my invention are reacted with amines or other alkalie s, are available on the market or are made by known methods. The amine salts themselves are considered to be new.

Examples of the surface active agents that may beused in my lotions are: the sodium salt of an alkyl aryl sulfonate, an example being one in which the alkyl group is dodecyl and the aryl is naphthyl, the sodium salt of keryl benzene sulfonate, sodium lauryl sulfate, ethylene oxide complex of a partial ester such as Tweens or spans, and the sodium salt of sulfated octadecyl alcohol.

There may be incorporated into the waving. lotion or solution conventional additives of which examples are perfuming, creaming, or coloring agents that are usual in hair treating compositions.

As to concentration, the salts of the thiocar: bonic acid esters are dissolved to a concentration of 5'to 15 parts by weight, usually 8 to 11, for 100 of water.

Compositions made as described are stable against oxidation in air, effective in waving hair with minimized danger of overtreatment, and of low or negligible odor.

The waving lotions are more active in softening keratin if the amine or other salt of the thiocarbonic and thiocarbamic acidesters selected for use is caused to stand for about one-half to 3 hours in solution in water before it is applied to the hair. This increase in effect is-considered by me to be due in part at'least to a change in degree of dispersion or change in solubility of thesolids in-water;

The invention will be further'illustrated-by detailed description in connection with the following specific'examples of the practice of it.

Example 1 9 g. of trithiocarbonic acid ester of glycolic acid of the formula somooon s=o somooon which is'a yellow crystalline solid having a melting point of 173-174" C. was dissolved in cc. of

water containing 5.5 g. monoethanolamine; A clear yellow colored odorless solution is formed having a pH of 9.25. I

The freshly prepared solution is applied on freshly sham'pooedhair, the hair'is wound on usual waving rods and preferably on those described in U. S. Patent No. 2,426,343, issued to me on August 26, 1947. After about 20 minutes to 1 hour, depending on the quality of the hair, the hair. is rinsed'with cold water, then with a dilute solution of hydrogen peroxide, again with water;

and then dried. The curl obtained is strongJan'd' the hair is soft and elastic.

Example 2 10.5 g. of the dithiocarbonic acid ester of glycolic acid of the formula ocmooon S 01120 OH which is a white crystalline solid having .a melting point of 136 C. was dissolved in 90 cc. of water containing enough hydroxyethyl ethylenediamine to bring the pH of the solution to 9.4. A small amount of an ionic surface active agent is added, such as sodium lauryl sulfate (Duponol C).

The solution was used on hair, vasdescribed for the other solution in Example 1-. The wave pro= duced by this. solution, in 30 minutes after preparation of the solution, was as strong as one produced with a solution containing thioglycolic acid with an excess of ammonia and other alkalies. The freshly prepared solution was yellowish in color, completely odorless, and the slight odor developed on longer standing was easily masked by the addition of a conventional perfume.

Example 3 Sodium salt of N diethyl dithiocarbamic acid ester of glycolic acid which has the formula N(C2Ht)2 S CHzC O ONa is easily prepared from sodium N diethyl dithiocarbamate and sodium monochloracetate and is a stable odorless crystalline solid. 9.2 g. of it was dissolved in 90 g. water then the pH of the solution adjusted to 9.3 with mixed isopropanolamines. The permanent wave produced with this solution in the steps described in Example 1 is long lasting and the hair is soft, lustrous and resilient.

Example 4 Ethylxanthogene acetic acid of the formula s on, o 0 OH is obtained by reacting potassium ethylxanthogenate with sodium monochloracetate and is a crystalline odorless solid having a melting point of 53-54" C. 9 g. of it was dissolved in 90 g. water containing enough morpholine to bring the pH of the solution up to 9.2. The freshly prepared solution was odorless. The Wave produced with the solution was equal to a wave produced using a 4.5% morpholine thioglycolate solution.

Example 5 The procedure of Example 1 is followed except that the thiocarbonic acid derivatives there described and representative of Formula 1 of the list given above is replaced by an equal weight of any of the other compounds of formulas given in the said list, namely, (2), (3), or (4) or by any other one of the thio esters referred to herein.

The solutions so made and neutralized by the alkali described in Example 1 are applied to hair and the steps given in Example 1 are followed. The result is a good wave.

Ewample 6 The procedure of any of the Examples 1-5 inclusive is followed except that the alkaline material used to neutralize the thiocarbonic acid derivative is replaced by any One of the amines described herein.

Example 7 The thio acid derivative of kind used in Examples 1-5 inclusive is mixed with a mineral salt of any one of the amines described herein as, for instance, the chloride, sulfate, borate or phos phate. The salt .is used in proportion to give aminecompo'nent at least equivalent to the free carboxyl groups of the thio acid ester used. This mixture is then treated before use in waving hair withv an amountv of lithium, sodium, or potassium hydroxide in amount equivalent to the said thio acid. The alkali and the mixture are dissolved together in water. .Or one of these materials may bedissolved the Water first. In any case the caustic alkali liberates sufiicient amine to form the amine salt of the thio acid used and it is the amine salt that is the active keratin softeningor waving ingredient.

Example 8 The procedure of any of the Examples1-7 is followed except that the amine therein is replaced by one of the caustic alkalies such as an alkali metal hydroxide, The caustic alkali is used in proportion to establish the pH of the aqueous solution at 8 to 10. In this composition there is included any one of the surface active agents shown above, as, for instance, the sodium lauryl sulfate in the proportion 0.1 part for 100 parts of the solution. j

Example 9 9 g. of the trithiocarbonic acid ester used in Example 1, 9 g. of monoisopropanolamine hydrochloride, and 3.4 g. of lithium hydroxide monohydrate were dissolved in 90 cc. of water at room temperature. The solution so obtained is odorless. It was applied to a freshly shampooed slightly moist hair in the form of strands and left in contact with the hair for various lengths of time ranging from minutes to 2 hours. After removal of the waving lotion by washing the hair in a dilute solution of potassium bromate, the dry hair was compared. None of the treated strands were over processed but all were lustrous and resilient.

Example 10 10.5 g. of the thiocarbonic acid derivative of Example 2 was dissolved in 90 cc. of water at C. together with 6.5 g. of anhydrous sodium carbonate and 0.75 g. ascorbic acid and 0.1 g. Tween. A clear odorless solution is formed which was applied on the hair for 1 hour.

The freshly prepared solution is then applied on freshly shampooed hair as described in Example 1.

Example 11 The procedure of Example 10 is followed except that the sodium carbonate thereof is replaced by any one of the amines disclosed herein, the amine being used in proportion 25% in excess of the chemically equivalent proportion of the sodium carbonate.

It will be understood also, that it is intended to cover all changes and modifications of the example of the invention herein chosen for the purpose of illustration which do not constitute departures from the spirit and scope of the invention.

What I claim is:

1. A hair waving composition comprising a 7 water soluble salt-01a water solubleamine with an alpha-hydro'xy fatty acid-ester of an acid selected from the group consisting of diand trithiocarbonic and dithiocarbamic acid and an excess of the water soluble amine in amount to establish a pH of at least/9.2, the said fatty acid containing 2110 4 carbon atoms to the molecule.

2. A hair waving composition as described in claim 1 including water in the'proportion of 100 parts by weight for 5 to15 partsof the said salt, the s'aid salt being the saltof a water soluble amine.

3. A hair waving composition comprising salt of a water soluble amine with a dithiocarbamic acid ester of an alpha-hydroxy fatty acid, the water soluble amine being used in excess of the amount required to form the salt and in proportion to establish-the pH of the composition within therange 8 to 10.

4. Acomposition as described in claim 1, the alpha-hydroxy fatty acid being g'lycolic acid.

5. A hair Waving composition comprising a water soluble salt of a water soluble aliphatic amine'with the ester of tr'ithiocarbonic' acid with an alpha-hydroxy fatty acid containing 2 to 4 ble amine in proportion to establish the pH withf m the range 8 to 10, the said may acid containing 2 to 4 carbonato'ms to the molecule.

7. A hair waving composition comprising an amine salt of a water soluble amine with a thiocarbonic acid ester of an alpha-hydroxy fatty acid and an excess of the water soluble amine in proportion to establish the pH within the range 8 to 10.

MENOTTI DEL ZOPPO.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,939,692 Hardman Dec. 19, 1933 1,973,130 Turley -Sept. 11, 1934 2,169,147 Jaeger Aug. 8, 1939 2,201,929 Speakman May 21,1940 2,238,672 Arthur Apr.-1 5, 1941 2,389,755 Baker Nov. 27, 194 5 2,405,166 Reed Aug. 6, 1946 2,418,664 Ramsey Apr. 8, 1947 2,442,461 Karrer June 1, 1948 FOREIGN PATENTS Number Country Date 117,071 Australia June 3, 1943 OTHER REFERENCES Holmberg, J. Prakt. Chemie, volume 71. (2nd Series) (1905), pages 269, 274 and 284, 285.

Holmberg, J. Prakt. Chemie, volume 79. (2nd Series) (1909), pages 257, 258, 263, 267, 268 and 269. v I

Bulletin 460, May 1942, Conn. Agr. Exp. Station, 34th Report on Drug Products, pages 448 to 450. 

1. A HAIR WAVING COMPOSITION COMPRISING A WATER SOLUBLE SALT OF A WATER SOLUBLE AMINE WITH AN ALPHA-HYDROXY FATTY ACID ESTER OF AN ACID SELECTED FROM THE GROUP CONSISTING OF DI- AND TRITHIOCARBONIC AND DITHIOCARBAMIC ACID AND AN EXCESS OF THE WATER SOLUBLE AMINE IN AMOUNT TO ESTABLISH A PH OF AT LEAST 9.2, THE SAID FATTY ACID CONTAINING 2 TO 4 CARBON ATOMS TO THE MOLECULE. 